【摘要】 酶-光偶联催化系统(EPCS)集成了半导体的光吸收能力和酶的高活性/特异性,可模拟自然界光合作用实现太阳能驱动的有用化学品合成.作为EPCS中的“能量货币”,辅因子(如NAD(P)+和NAD(P)H)参与了约80%的酶促氧化还原反应,且在酶-光间充当物质/能量交换的枢纽.然而, EPCS涉及光催化和酶催化反应,涉及分子、电子和质子传递过程,属于典型的复杂多相反应,导致其光-化学转化效率与理论值差距较大.本文从微观尺度对EPCS中分子-电子-质子传递过程进行了理解和剖析,系统介绍了自然界光合作用和EPCS中的“新三传”(即质量传递、热量传递和动量传递)现象.与传统化工领域通过强化宏观尺度上“三传”提升单元操作过程效率的方法类似,本文总结并提出了通过协调优化“新三传”(即分子传递、电子传递和质子传递)来强化EPCS中物质-能量耦合关系,进而提升光-化学转化效率的新策略.其中,分子传递主要包括电子供体分子从反应液向催化剂传递以及辅因子分子在光催化模块和酶催化模块间穿梭;电子传递主要包括光生电子从其生成位点到光催化剂表面进而到电子媒介的传递;质子传递主要包括质子从溶液或催化剂表面向电子媒介的传递.期望通过“新三传”强化EPCS效率的理念,打破自然界光合作用的局限,实现温和条件下多种功能分子的高效合成,为人工光合与绿色生物制造领域提供新思路.更多还原

【Abstract】 Enzyme-Photo-coupled Catalytic System(EPCS) integrates the light absorption capacity of photocatalysts and the high activity/specificity of enzymes, which is becoming an emerging technology platform to mimic natural photosynthesis for harnessing solar energy to generate valuable products, including bulk chemicals, energy chemicals and pharmaceutical chemicals. Cofactors including NAD(P)+/NAD(P)H, as "energy currency", are involved in over 80% biocatalytic redox reactions, establishing a bridge of mass/energy exchange between photocatalysis and cofactor–dependent enzyme catalysis. Although numerous efforts have been devoted, the performance of current EPCS is far from the theoretical upper limit. The individual and synergistic intensification of molecule-electron-proton transfer evolves a critical yet challenging issue in EPCS. This Review will focus on the molecule-electron-proton transfer in natural photosynthesis and in EPCS. Future endeavors to intensify all three transfers to construct a more efficient EPCS are suggested as pursuit for a new pattern of modern chemical engineering.更多还原